Vinyl phenol copolymers



rni niea a... 29,1952

VINYL manor. coroLYMens Edward Michael Evans; Tonbridge, England, and John Edward Seazer Whitney, Penarth, Wales, suignors to British Resin Products Limited,

London, England, a British company No Drawing. Application February 1, 1950, se-

rial No. 142,949. In Great Britain February The present invention relates to the polymerisatlon of vinyl phenol-type compounds and has as object the production 01' copolymers thereof with cyclopentadiene and indene-type subces.

' the preliminary exothermic reaction had ceased,

9 Claims. CI. 26047) the mass was heated for 8 hours at 100 to form a reddish-brown thermoplastic resin. on heating this resinwith 12% hexamethylene tetramine at 120 C. it rapidly became insoluble and infusible. polymerisation of vinyl phenols is known 8 i Example an t e polymerisation oi cyclo-pentadieneand indene-type substances is also known, butthe c og i fig z g igg gwmg g g fg gt polymerisation or mixtures these two types of dominantly indene and Zoumarone 11 parts of monomer has not previously been described metavinyl phenol and 1 part or activated i'ullers we have now mund that by subjecting earth (No. 249 as supplied by The Fuller's Earth tures of vinyl plienol'type compounds and W010 Union Ltd.) was refluxed at atmospheric prespenmdiene and/w indem'type sure with stirring roi- 50 hours. At the conclupolymerisation conditions copolymers are formed, slon of this period the unpolymemd material 7 the molecules of which contain units oi-each'type. 15 was removed by steam distillation at reduced Amongst the polymerisation initiators found to pressure to leave a brown thermoplast which be suitable are Strong mineral acids such as could be rendered iniusible-and insoluble by heatdrochloric and sulphuric acids, acid activated mg with of hexamethylene utmmme at clayahstannic chloride, boron trifiuoride and C a phosp orusoxy chloride and heat. Polymerisa- The resins of this invention may be used catalysts of the weaker type Such as a basis for lacquers or moulding powders and ganic peroxy compounds, aluminium chloride and may if desired be subjected to the cross linking ugmfiviolet light may also be used but are less and/or etheriflcation treatments disclosed in our e co ve a u co endin a licatlons, Serial No. 127,783, filed By vinyl pheml'type meant the 2 No zlembei 15 1949, and Serial No. 127,784, filed ortho-, metaand para vinyl phenols and their November 16 9 lower nuclear homologues, such as the methyl, What weciaim ethyl and propyl substituted derivatives, which 1 A process as forth m claim 8' wherein i by deilydrogenation a i the polymerisation initiator employed is selected one mg 0 p 3, Subst tuted open cham 110 from the group consisting of strong mineral acids. drocarbons. By cyclopentadiene and/orindeneac1d activated clays stanmc chloride boron trb type compound is meant eyclopentadiene. influoride and phosphbrus Oxychloride dene and coumarone and their polymerisable 2 A process as set forth in clam; 1 wherein lower homologues, such as polymerisable methyl bhe'polymerisaflon is assisted by heat and ethyl substituted derivatives, and the proc- 3 A recess as forth in wherein ess oi. the present invention extends also to the g phenol compound is memwmgq phenol treatment of materials such as naphthafractions 4 A process as set forth in claim 8 wherein which contain substantial proportions of these i Substance is cyclopentadlene compounds.

- 5. A process as set forth in claim 8, wherein The following examples illustrate two embodiments of this invention, the parts referred to 40 said substance constitutes part of a naphtha being by weight. fraction 4 Example 1 6. A metavinyl phenol-cyclopentadiene c0- A polymer. To parts 01 monomeric cyclopentadiene, 7. A metavinyl phenol-coumarone indene coprepared by distillation of the dimer, were added polymer. 4 50 parts of meta vinyl phenol and, after thor- 8. A process for the production of a synthetic ough mixing, 2.5 parts'ot stannic chloride were resin which comprises copolymerising a vinyl added at such a rate that the temperature of the phenol compound, by subjecting it to the action reacting mass did not rise above C. When 0 of a polymerization initiator, said compound being selected from the group consisting of ortho,

meteand paravinvl phenol and their lower nusisting of .cyclopentadiene, indene. coumarone and their polymerisabie lower homologues.

EDWARD MICHAEL EVANS. 1 JOHN EDWARD .S EAGER WHITNEY. I

'REFERENCES crmn The iollowing references are of record in the file of this patent: v

tmn'mn STATES PATENTS Number Name Date 1,754,052 Ro'aenthal Apr. 8, 1930 2.499.865 De Groote Mar. L 1950 

9. A COPOLYMER OF A VINYL PHENOL COMPOUND SELECTED FROM THE GROUP CONSISTING OF ORTHO, META AND PARA VINYL PHENOL AND THEIR LOWER NUCLEAR HOMOLOGUES HAVING AT LEAST ONE UNSUBSTITUTED REACTIVE HYDROGEN ATOM ATTACHED TO THE NUCLEUS, WITH A SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF CYCLOPENTADIENE, INDENE, COUMARONE AND THEIR POLYMERISABLE LOWER HOMOLOGUES. 